CN101177079B - Method for printing micro contact pattern with hydrogel as template and colloid crystal as writing ink - Google Patents
Method for printing micro contact pattern with hydrogel as template and colloid crystal as writing ink Download PDFInfo
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- CN101177079B CN101177079B CN 200710191072 CN200710191072A CN101177079B CN 101177079 B CN101177079 B CN 101177079B CN 200710191072 CN200710191072 CN 200710191072 CN 200710191072 A CN200710191072 A CN 200710191072A CN 101177079 B CN101177079 B CN 101177079B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
Abstract
The invention relates to a micro contact pattern printing method with hydrogel as template and colloid and crystal as ink, comprising the steps that: diluting monodisperse silicon dioxide, or polystyrene, or polymethyl methacrylate microspheres with deionized water; evenly diluting and mixing the mixture of acrylamide and methylene bisacrylamide with a rate of mass to volume of 10% to the rate of3% to 6% while adding an initiator azobisisobutyronitrile; obtaining hydrogel through irradiation and polymerization for 40 minutes by a high-voltage mercury lamp under four DEG C; peeling the hydrogel off a die, sufficiently washing the hydrogel and storing the hydrogel in pure water of four DEG C; immersing the prepared template into colloid and crystal solution, lifting and pulling the templateby a lifting-pulling machine, facilitating the formation of self-assembled colloid and crystal foil and waiting for the foil dried under ambient temperature, and softly making a hydrogel template with patterns formed in the second step contact with a substrate of hydrophobic material of the coating layer with colloid and crystal, removing the template, and an orderly colloid and crystal being transferred to the surface of the substrate.
Description
Technical field
The invention describes a kind of method for printing patterns of novel easy little contact, this method is based on that colloidal crystal spatial micro-contact printing of transferring on another template on the hydrogel template forms.With respect to being that template carries out being that template is not only very easy with the hydrogel, and accessing good printing effect and have good practicability for the micro-contact printing with other materials.
Background technology
Diameter is that sub-micron, monodispersed inorganic or polymeric colloid microballoon can self assembly form two dimension or three-dimensional orderly arrangement under the effect of gravity, electrostatic force or capillary force.These microsphere aggregation bodies of arranging in order are commonly called colloidal crystal or synthetic proteins stone.Colloidal crystal is a kind of of photonic crystal, and this class material all is being widely used aspect electronics, optics and the bio-sensing.
The patterned print of micro-nano-scale has been called the focus of present age research, and the development of many new technology industries is all from the patterned process of new microstructures.Micro-fluid chip for example, its micro-processing technology also are to use to use for reference in the very ripe silicon lithographic printing from microelectronic industry to come at first.Have, as chemical analysis and biological detection, the patterned surface technology also provides possibility for the repercussion study that takes place in these micro-nano-scale scopes again.Along with patterned surface technology and potential application and development thereof, emerged many physical chemistry and the patterned surface on the biology in recent years and used.Thus, people can realize research and the control to the various character of material on small scale.Soft lithography is the most extensive so far, the patterned surface technology of reliable non-photoetching.Soft lithography is that the Whitesides research group by Harvard University in 1993 at first develops, and relates to the general designation of a class integrated technology in fields such as conventional lithography, organic molecule self assembly, electrochemistry, polymer science.Soft lithography has comprised the method for a series of patterning materials flexibly.Mainly contain micro-contact printing, duplicating molded, micrometastasis molding, the interior little molding of capillary and solvent and assist little molding.In these methods, little molding has been applied directly to the patterning colloid crystal in the capillary.Based on different interaction forces, as covalent bond, electrostatic interaction, physical absorption etc., many materials can carry out patterning with the method for micro-contact printing on solid substrate.
Hydrogel (Hydrogel) is a kind of macromolecule network system, and the character softness can keep certain shape, can absorb a large amount of water.Every water-soluble or hydrophilic macromolecule by certain chemical crosslinking or physical crosslinking, can form hydrogel.These macromolecules can be divided into natural and synthetic two big classes by its source.Natural hydrophilic macromolecule comprises polysaccharide (starch, cellulose, alginic acid, hyaluronic acid, shitosan etc.) and polypeptide class (collagen, poly-L-lysine, poly-L-GLU etc.).Synthetic hydrophilic high mol comprises acrylic acid and derivative class thereof (polyacrylamide, poly-N-is poly-for acrylamide etc. for polyacrylic acid, polymethylacrylic acid).As the high water-keeping material of a kind of high suction, hydrogel is widely used in multiple field.
Asher group has prepared the colloidal crystal gel in 1994, this is a kind ofly not only to have the optical property of photonic crystal but also have the environmental response of hydrogel and the new material of shape memory characteristic.When the hydrogel skeleton with after specific recognition component combines, recognition component and corresponding aglucon effect meeting cause the expansion or the contraction of gel rubber system.The lattice paprmeter that this has changed the colloidal crystal gel is moved the diffraction maximum of colloidal crystal gel.Utilize the environmental sensitivity and the Memorability of hydrogel, the concentration of the corresponding aglucon of mutation analysis of diffraction maximum position that can be by measuring the colloidal crystal gel.Asher group has set up to sensing materials such as metal ion, glucose and pH and optical switch material etc.Except that Asher group, also have two groups to carry out the research of colloidal crystal gel aspect, Sawada group and Foulger group.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of is that template and colloid crystal is that ink carries out little contact patterns method of printing with the hydrogel, this method can provide an easy approach for the substance transfer in the micro-contact printing technology, but also can be extended to micro-contact printing The Application of Technology scope based in the colloidal crystal field.
Technical scheme: purpose of the present invention can realize by following scheme: adopt the monodisperse silica microspheres of sol-gel process preparation and carry out self assembly with the polystyrene microsphere that the suspension emulsion polymerization prepares to prepare orderly colloidal crystal, utilize it to be self-assembled into the structure that ordered structure realizes its pattern transfer then on hydrogel template.
This method comprise preparation, the hydrogel template of orderly colloidal crystal preparation, scribble four steps of micro-contact printing of colloidal crystal film, colloidal crystal,
1. the preparation of colloidal crystal in order: with monodispersed silica or polystyrene or poly (methyl methacrylate) micro-sphere, add the deionized water dilution, quality of regulation percentage is that 0.5%-2.0% is standby,
2. the preparation of hydrogel template: mass volume ratio is that to be diluted to volume ratio be 3%-6% for 10% acrylamide and methylene diacrylamide mixed liquor, after adding the different dibutyronitrile mixing of initator azo, feed nitrogen 2-4min or vacuum outgas 2-4min, pour in the mould, leave standstill 20min; 4 ℃ of following high voltage mercury lamp radiation polymerization 40min promptly get hydrogel, and it is peeled off from mould, and fully wash to be placed in 4 ℃ of pure water with pure water and preserve,
3. scribble colloidal crystal film: the template for preparing is immersed in the colloidal crystal solution, lifts, be self-assembled into colloid crystal film, treat that it is at room temperature dry at template surface with lifting instrument,
4. the micro-contact printing of colloidal crystal: the hydrogel template that has patterning that forms in 2. in step and the hydrophobic material substrate of the coating that scribbles colloidal crystal contact gently, then template is removed, orderly colloidal crystal just has been transferred on the surface of substrate.
The colloidal crystal coating is a silica, or polystyrene, or polymethyl methacrylate.
In acrylamide and the methylene diacrylamide mixed liquor, calculate acrylamide: methylene diacrylamide=29: 1 with mol ratio.
The different dibutyronitrile mass volume ratio of initator azo that adds is 1%.
In the present invention, we improve and have developed the micro-contact printing technology, introduce hydrogel as template, simple and efficient preparation template, form colloid crystal film in its surperficial self assembly then, slightly contact with it with any material substrate, thereby realized the transfer of colloidal crystal microballoon on solid substrate, just realized the colloidal crystal micro-contact printing.
Beneficial effect: this method can provide an easy approach for the substance transfer in the micro-contact printing technology, but also can be extended to micro-contact printing The Application of Technology scope based in the colloidal crystal field, further promote development new material and device.
Description of drawings
Fig. 1: the schematic diagram of realizing the patterning of colloidal crystal on hydrogel template with the micro-contact printing technology;
The specific embodiment
Embodiment 1:
1, the preparation method of silicon dioxide microsphere: select for use the reinforced method of quick clearance-type to prepare monodispersed SiO
2Nano microsphere.The ammoniacal liquor of 88ml absolute ethyl alcohol and 3.2ml ethyl orthosilicate mixed liquor and 20ml and 88ml absolute ethyl alcohol mixed liquor join in the flask, and begin simultaneously to stir, and rotating speed is 350 rev/mins; Add 16ml ammoniacal liquor then; Add 176ml absolute ethyl alcohol and 4ml ethyl orthosilicate mixed liquor after 5-10 minute.React after 2 hours, can obtain the good Nano particles of silicon dioxide of monodispersity.Temperature by changing water bath can fine control silica particle diameter.
2, the preparation of hydrogel template: 10% (mass volume ratio) acrylamide and methylene diacrylamide mixed liquor (acrylamide: methylene diacrylamide=29: 1, mol ratio) dilutes most 3%-6% (volume ratio), add the different dibutyronitrile (1% of initator azo, mass volume ratio) behind the mixing, feed nitrogen 2-4min or vacuum outgas 2-4min, pour into (above operation is all carried out) in the mould quiet stomach 20min in medical clean work station.4 ℃ of following high voltage mercury lamp radiation polymerization 40min promptly get hydrogel.It is peeled off from mould, fully wash to be placed in 4 ℃ of pure water with pure water and preserve.
3, use is with the micro-contact printing technology of hydrogel template, realize that the parallel band of silicon dioxide microsphere colloidal crystal is from the enforcement of hydrogel template to the transfer of planar substrates: regulating silicon dioxide microsphere quality of the emulsion percentage concentration is 0.5-2.0%, the hydrogel template for preparing is immersed in the above-mentioned colloidal crystal solution for preparing, lift with lifting the speed of instrument with 30 μ m/s-60 μ m/s, be self-assembled into colloid crystal film at template surface, treat that it is at room temperature dry.After treating its drying, slightly contact with template with the substrate of another material, the colloidal crystal film of template surface just has been transferred on the surface of substrate.Treat to form pattern model after the substrate surface drying with color.
Embodiment 2:
1, the preparation method of polystyrene microsphere: under nitrogen protection, with 10ml styrene, the methacrylic acid of 225ml ultra-pure water and 1ml adds in the three-necked bottle, stirs 350r/min.Be warming up to 70 ℃, stable back adds the 0.32g potassium peroxydisulfate as initator, reacts 10h at least, can obtain particle diameter and be the polystyrene microsphere about 245nm.
2, the preparation of hydrogel template is as described in the example 1.
3, use is with the micro-contact printing technology of hydrogel template, realize that polystyrene microsphere colloidal crystal five-pointed star pattern is from the enforcement of hydrogel template to the transfer of planar substrates: regulating polystyrene microsphere quality of the emulsion percentage concentration is 0.5-2.0%, the hydrogel template for preparing is immersed in the above-mentioned colloidal crystal solution for preparing, lift with lifting the speed of instrument with 30 μ m/s-60 μ m/s, be self-assembled into colloid crystal film at template surface, treat that it is at room temperature dry.After treating its drying, slightly contact with template with the substrate of another material, the colloidal crystal film of template surface just has been transferred on the surface of substrate.Treat to form pattern model after the substrate surface drying with color.
Embodiment 3:
1, the no soap suspension polymerization under boiling temperature is adopted in the preparation of the preparation of polymethyl methacrylate (PMMA) microballoon: PMMA.Be briefly described as follows, the methyl methacrylate of 40ml is put into arrow-necked bottle, add the methacrylic acid of 0.1ml and the ultra-pure water of 150ml, be heated to boiling, seething with excitement added the initator potassium persulfate in back 5 minutes, reaction 1.5h.The particle diameter of microballoon can be controlled by the amount of monomer that adds.
2, the preparation of hydrogel template is as described in the example 1.
3, use is with the micro-contact printing technology of hydrogel template, realize that polymethyl methacrylate (PMMA) microballoon colloidal crystal triangle pattern is from the enforcement of hydrogel template to the transfer of planar substrates: regulating polystyrene microsphere quality of the emulsion percentage concentration is 0.5-2.0%, the hydrogel template for preparing is immersed in the above-mentioned colloidal crystal solution for preparing, lift with lifting the speed of instrument with 30 μ m/s-60 μ m/s, be self-assembled into colloid crystal film at template surface, treat that it is at room temperature dry.After treating its drying, slightly contact with template with the substrate of another material, the colloidal crystal film of template surface just has been transferred on the surface of substrate, treats to form the pattern model with color after the substrate surface drying.
Claims (4)
1. one kind is that template and colloid crystal is that ink carries out little contact patterns method of printing with the hydrogel, it is characterized in that this method comprise preparation, the hydrogel template of orderly colloidal crystal preparation, scribble four steps of micro-contact printing of colloidal crystal film, colloidal crystal
1. the preparation of colloidal crystal in order: with monodispersed silica or polystyrene or poly (methyl methacrylate) micro-sphere, add the deionized water dilution, quality of regulation percentage is that 0.5%-2.0% is standby,
2. the preparation of hydrogel template: mass volume ratio is that to be diluted to mass volume ratio be 3%-6% for 10% acrylamide and methylene diacrylamide mixed liquor, after adding the different dibutyronitrile mixing of initator azo, feed nitrogen 2-4min or vacuum outgas 2-4min, pour in the mould, leave standstill 20min; 4 ℃ of following high voltage mercury lamp radiation polymerization 40min promptly get hydrogel, and it is peeled off from mould, and fully wash to be placed in 4 ℃ of pure water with pure water and preserve,
3. scribble colloidal crystal film: the hydrogel template for preparing is immersed in the colloidal crystal solution, lifts, be self-assembled into colloid crystal film, treat that it is at room temperature dry at template surface with lifting instrument,
4. the micro-contact printing of colloidal crystal: the hydrogel template that has patterning that forms in 3. in step and the hydrophobic material substrate of the coating that scribbles colloidal crystal contact gently, then template is removed, orderly colloidal crystal just has been transferred on the surface of substrate.
2. as claimed in claim 1 is that template and colloid crystal is that ink carries out little contact patterns method of printing with the hydrogel, and it is characterized in that: the colloidal crystal coating is a silica, or polystyrene, or polymethyl methacrylate.
3. as claimed in claim 1 is that template and colloid crystal is that ink carries out little contact patterns method of printing with the hydrogel, it is characterized in that: in acrylamide and the methylene diacrylamide mixed liquor, calculate acrylamide: methylene diacrylamide=29: 1 with mol ratio.
4. as claimed in claim 1 is that template and colloid crystal is that ink carries out little contact patterns method of printing with the hydrogel, it is characterized in that the different dibutyronitrile mass volume ratio of the initator azo that adds is 1%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200710191072 CN101177079B (en) | 2007-12-07 | 2007-12-07 | Method for printing micro contact pattern with hydrogel as template and colloid crystal as writing ink |
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| CN 200710191072 CN101177079B (en) | 2007-12-07 | 2007-12-07 | Method for printing micro contact pattern with hydrogel as template and colloid crystal as writing ink |
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| CN101177079B true CN101177079B (en) | 2010-06-02 |
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| CN102653190A (en) * | 2011-03-04 | 2012-09-05 | 国家纳米科学中心 | Method for forming graphene oxide pattern and graphene pattern |
| CN102560643B (en) * | 2011-12-29 | 2015-09-30 | 广东爱康太阳能科技有限公司 | A kind of template for the preparation of colloidal crystal and make the processing method of this template |
| CN102643448B (en) * | 2012-03-29 | 2014-06-25 | 上海师范大学 | Preparation method and application of temperature-sensitive patterned polymer surface with orientation structure |
| CN105780102B (en) * | 2016-04-28 | 2018-08-03 | 河南大学 | A kind of device of quick preparation mono-/bis-member two-dimensional colloidal crystal |
| CN105947970A (en) * | 2016-05-16 | 2016-09-21 | 华南师范大学 | Ordered large-area single-layer microspheres/nanospheres assisted by template and preparation method thereof |
| CN107417945B (en) * | 2016-05-23 | 2020-03-13 | 中国科学院长春应用化学研究所 | Micro-nano ordered array structure and preparation method thereof |
| CN112229826A (en) * | 2020-08-31 | 2021-01-15 | 广东比派科技有限公司 | Universal high-efficiency multi-substrate detection photonic crystal microchip |
| CN113009598B (en) * | 2021-03-05 | 2022-03-18 | 吉林大学 | Method for improving water/mechanical stability of opal photonic crystal film |
| CN113985505A (en) * | 2021-10-21 | 2022-01-28 | 浙江大学 | Method for preparing micro-lens array based on hydrogel microstructure template |
| CN115947888A (en) * | 2022-10-14 | 2023-04-11 | 浙江理工大学 | Preparation method of rapid temperature-sensitive response polyacrylamide composite hydrogel |
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